Phosphoric acid derivatives and methods of preparing the same



i new organic compounds.

Patented Aug. 12, 1952 asoesoo PHOSPHORIC ACID DERIVATIVES f METHODS OF PREPARING THESAME Robert P. Parker, Somerville, Doris Bound Brook, and Erwin Kuh, New

assignors to American-Cyanamid G orn- I V R. Seeger, Brunswick,-.

pany, cw ork,-N .--Y,,-a. corporation of Maine j 'Noljrawinsf jlflilication July 25, 1951,

Serial N0. 238,581

This invention relates 'to" the preparation of relates to phosphoric acid triamides and methods for their preparation It is well known in'the prior art to prepare phosphoric acid triamide and its N,N',N"-trialkyl-, triaralkyl-, triaryla-nd-tripentamethylene substituted derivatives'(G. M. Kosolopoif, Organophosphorouscompounds; 1950, pages 312-315).

The compounds of the present invention, in contrast to those of the prior art, are N-substituted N ',N' -diethylenep'hosphoric triamides which may contain certain substituents on a ring-carbon atom of the ethylenimine rings.

They may be represented by. the following fora I m'ula:

in which R. represents hydrogen ora rac licalof the aliphatic, aliphatic-aromatic or aromatic series, and R represents a radical of the aliphatic or cycloaliphatic series containing at leastfour carbon atoms. 1 Y i The compounds of vthepresent invention possess chemically reactive ethylenimine rings mab' ing them useful as textile chemicals; they may be polymerized to yield new plastics. However, it is surprising that the compounds of the present invention which contain thehighly reactive ethylenimine' ring are so stable that they may be used as therapeutic agents.

The compounds of the present invention are, in general, low melting solids to viscous liquids. While some of the lower members are water-soluble; as a class they are soluble in organic solvents and the higher members of the series possess marked lipid' -s'olubilityi-fi. i

These compounds are-prepa J .daby-starting with a trihalophosphoric acid-asuch' :as? phosphorous More particularly, it

. sl fi s. .(Cl. mil- I t oxychloride or phosphorous oxybromide which is first reacted with a molecular equivalent of a secondary dialiphatic or dicycloaliphatic amine which replaces one of the halogen atoms. This intermediate monoamidodihalophosphoric acid is m n thy e y m flrpropy ethyle mine; Z-hexylethylenimine; 2-diethy-lethylenithen reacted with two-molecular equivalents of an ethyl'enimine compoundito produce; the desired phosphoric acid triamides of thepresent inven: tion. These reactionsmay berillustrated by the .7 following general equationsz,

n i h s ch o ine; o i. rQm nea-nd:B-:anc1: R3- are as previously; defined=1;,I-n; this;reaction"the c nda yid a inhat c"or .dic q o linh ie-amin usedi irthefi z tzste rmay;bean: nesmha a; d m-b -y a n ld is qu -vlam ne' amylamirie.:

d e cylamneq qod cylaminen tizmexnamme;

a d= he vlike -Theae gyilenimines used in? e; ccndsten m b -cqmpqua sz u as.ethyleni mine; tsel pr; .Gzsu st tut lz e yl sim csx u :m h lel-iv en zm :2;. :e me h let y1e ine; Zi e e -zrnhcnyl th en min ;;:grphe y ethylenimine. These ethylenimine i termediatea may be prepared by known procedures such as 1 by ring closure with" an alkali metal hydroxide of the corresponding Z-haloethylamihe or sulfuric ester of the corresponding 2-hydroxyethylamine.

The reaction to prepare theiconipounds of the present inventionis preferably carried out in an organic solvent such asfbenfzene, ether, dioxane, and the like in'the presence of a tertiary amine as acid acceptor such as triethylamine, N-ethylmorpholine or pyridine. The reaction can also be carried out in aqueous solution, and under these circumstances, the acid acceptor may be an ke ieesesam -su h aeeealke kmetal; can; e r 'ieeeee fal r.

a eat-P s carried. out at afiem-pratur it the range of;

the reaction is generally complete within a period of a few minutes up to several hours. Isolation of the product from organic medium may be accomplished by filtration of the tertiaryamine hydrochloride salt and crystallization from the solvent or by evaporation of the organic solvent. If prepared in aqueous medium some members may be isolated by filtration, others must be extracted from the aqueous solution by the use of organic solvents. The procedure will vary with the individual members according to their solubility properties. 7

The following examples illustrate the preparation of the phosphoramides of the present invention. All parts are by weight unless otherwise indicated.

EXAMPLE 1 N,N-diisobutyZ-N' ,N -dimethylenephosphoric triamide A solution of 24.2 parts of N,N-diisobutylamidodichlorophosphoric acid in 100 parts of dry benzene is added slowly to a mixtur of 9.85 parts of ethylenimine, 21.65 parts of triethylamine and 100 parts of dry benzene at 10 C. Agitation is continued for an additional three hours without cooling, after which the triethylamine hydrochloride is filtered off. Benzene is' removed under reduced pressure, and the residue solidifies upon cooling. After recrystallization from benzene the white crystalline product melts at 78-'79 C.

EXAMPLE 2 20 parts of di-n-octylamine and 8.4 parts of triethylamine are dissolved in 65 parts of dry benzene. To. this is added slowly with agitation 12 parts of,phosphorus oxychloride dissolved in 65 parts of dry benzene at 5 to C. The mixture is allowed to come to room temperature and stirred for two hours more. The triethylamine hydrochloride is filtered off and washed with benzene. From the filtrate the benzene is removed by distillation under reduced pressure.

parts of the crude N,N-dioctylamidodichlorophosphoric acid is redissolved in 50 parts of dry benzene and added slowly to a solution of 11.4 parts of triethylamine and 4.8 parts of ethyleniminein 65 parts of dry benzene at 5 C. The reaction mixture is allowed to reach room temperature and'the benzene is removed under reduced pressure. The product then distills at 168 at 0.3 mm. of mercury.

We claim:

1. Compounds of the group having the general formula:

in which R is a member of the group consisting of hydrogen and lower alkyl radicals and R is an alkyl radical containing 4 to 12 carbon atoms, inclusive.

2. Compounds of the group having the general formula:

CH RI triamide.

4. N,N dioctyl N,N" diethylenephosphoric triamide.

5. A method of preparing compounds having the formula:

R r v R in which R is a member of the group consisting of hydrogen and lower alkyl radicals and R is an alkyl radical containing 4 to 12 carbon atoms inclusive which comprises reacting a compound havin the formula:

in which X is halogen and R is as defined above with at least two molecular equivalents of a compound having the formula:

HN R

in which R is as defined.

6. A method of preparing compounds having the formula:

P on N',N" -diethylenephosphoric triamide The following references are file of this patent:

REFERENCES CITED of record in the UNITED STATES PATENTS Number Name Date Dreyfus June 6, 1939 Adams et al Mar. 27, 1945 

1. COMPOUNDS OF THE GROUP HAVING THE GENERAL FORMULA: 